1-phenoxy-and 1-phenylthio-anilino-4-hydroxy-anthraquinone dyes



United States Patent 3,278,563 l-lHENOXY- AND 1-PHENYLTHIO-ANILINO-4- HYDROXY-ANTHRAQUINONE DYES Peter Hindermann, Basel, Hans Peter Kolliker, Munchenstein, Basel-Land, and Alfred Staub, Binningen, near Basel, Switzerland, assignors to J. R. Geigy, A.-G., Basel, Switzerland No Drawing. Original application Apr. 22, 1963, Ser. No. 274,779, new Patent No. 3,214,445, dated Oct. 26, 1965. Divided and this application May 25, 1965, Ser. No. 473,259

Claims priority, application Switzerland, Apr. 26, 1962,

5,026/62; July 24, 1962, 8,908/62 7 Claims. (Cl. 260-380) This application is a division of our copending application, Serial No. 274,779, filed April 22, 1963.

The present invention concerns substituted dihydroxyphenylamino-anthraquinones, processes for the production thereof, dyeing processes using these new anthraquinone dyestuffs, as well as, as industrial product, the material fast-dyed with the aid of these dyestuffs.

The known l-phenylamino-4-hydroxy-anthraquinone dyestuffs which have been used in the dyeing of acetate rayon are often not satisfactory for the dyeing of polyester fibers because of their inferior drawing power on the latter fibers, and the lack of fastness to light and to sublimation of the resulting colored fibers.

It is, therefore, an important object of the invention to provide 1-phenylamino-4-hydroxyanthraquinone dyes which draw well especially on polyester fibers and afford colored materials which are distinguished by good fastness, particularly to sublimation.

It has been found that valuable, difficulty water-soluble dihydroxy-phenylamino-anthraquinones of formula n represents a positive integer of at most 4,

2) wherein:

are obtained if a dihydroxydinitro anthraquinone of formula in ti NO: (11) wherein Y and Y have the meanings given in Formula I, is reacted with an amine of Formula III (III) ice wherein Z, R, R R and n have the meanings given in Formula I and the product obtained, if desired, is afterhalogenated.

When R is a lower alkyl group it is preferably the methyl group but it can also be an ethyl group; if R is halogen then it is, for example, chloride or bromine.

Because of their easy accessibility, dyestuffs of Formula I in which n is 1 or 2 and Z is oxygen are preferred.

Dihydroxydinitro anthraquinones of Formula II used according to the invention as starting materials can belong to the 1,5-dihydroxy anthraquinone series (anthrarufin) or the 1,8-dihydroxy anthraquinone series (chrysazin); often mixtures of these isomers can also be used with advantage in the process according to the invention.

Examples of amines of Formula III to be reacted according to the invention are: 3-amino-diphenyl ether or thioether, 4-amino-diphenyl ether or thioether, 3-amino-2'- methylor 2-ethyl-diphenyl ether or thioether, 3-amino- 3-methylor 3-ethyl-diphenyl ether or thioether, 3- amino-4'-methylor 4-ethyl-diphenyl ether or thioether, 4-amino-2-methylor 2'-ethyl-diphenyl ether or thioether, 4-ami-no-3-methylor 3'-ethy1-diphenyl ether or thioether, 4-amino-4-methylor 4'-ethyl-diphenyl ether or thioether, 3-amino-2-chloroor 2'-bromo-di henyl ether or thioether, 3-amino-3'-chloroor 3'-bromo-diphenyl ether or thioether, 3-amino-4'-chloroor 4'-bromo-diphenyl ether or thioether, 4-amino-2'-chloroor 2-bromo-diphenyl ether or thioether, 4-amino-3'-chloroor 3-brorno-diphenyl ether or thioether, 4-amino-4'-chloroor 4'-bromo-diphenyl ether or thioether, 3-amino- 3',5-dirnethyl-diphenyl ether or thioether, 4-amino- 3',5-dimethyl-diphenyl ether or thioether, 4-amino-3'-chloro-4'-methyl-diphenyl ether or thioether, 4-amino-3,S-dimethyl-diphenyl ether or thioether, 4-amino-3,5,4-trimethyl-diphenyl ether or thioether, 3-amino-2,4-dimethyl-diphenyl ether or thioether, 4-an1in0-2,3,5,6-tetramethyl-diphenyl ether or thioether, 4-amino-3,S-diethyl-diphenyl ether or thioether or 4- amino-3-methyl-5-ethyl-diphenyl ether or thioether.

Because of their greater stability under the reaction conditions, the aminodiphenyl oxygen ethers are preferred to the corresponding thioethers.

These amines are obtained, for example, by condensation of a p-nitro-halogen benzene which can also contain lower alkyl groups, with an unsubstituted or an alkyland/ or halogen-substituted hydroxyor mercapto-benzene to form the corresponding nitrodiphenyl ether or thioether followed by reduction of the nitro group to the amino group; they are also obtained by condensation of an m-bromoaniline with a hydroxyor mercapto-benzene of the type mentioned above in the presence of copper. I

The reaction of the reaction partners to form compounds of the Formula I is performed in an excess of amine in the melt at -200 C., advantageously however, in an inert organic solvent boiling at to 200 C., e.g. in butanol, glycol monoethyl ether, dimethyl formamide or, especially, in a preferably substituted hydrocarbon such as chlorobenzene, dichlorobenzene and, in particular, nitrobenzene.

When the new dihydroxyphenylamino anthraquinones are to be after-halogenated, this is performed advantageously with elementary chlorine or bromine or with sulfuryl chloride in a solvent which is inert to halogen such as nitrobenzene or chloroform or also in sulfuric acid.

The new dihydr-oxyphenylamino anthraquinones of Formula I' generally crystallize out of the reaction mixture. They are obtained by filtration, dilution of the mixture with water or a lower alkanol or by removal of the organic solvent by distillation or steam distillation and they can be purified by recrystallization.

In the pure state, the new dyestuffs of Formula I are bronzy, crystalline, deeply colored compounds. They dissolve in hot organic solvents with a pure blue color.

Fibers made from polymeric esters of aromatic polycarboxylic acids and polyvalent alcohols which can be dyed according to the invention are, e.g.: Terylene of Imperial Chemical Industries, Manchester; Dacron of E. I. du Pont de Nemours & Co., Wilmington, Delaware, U.S.A.; Tergal of Rhodiaceta, Lyons; Trevira of Farbwerke Hoechst, Frankfurt am Main; Terital of Rhodiatoce, Milan; or K-odel of Eastman Chemical Products, Inc., Kingsport, Tenn., U.S.A.

Fibers made from polymeric esters of aromatic polycarboxylic acids and polyvalent alcohols are dyed with the aqeous dispersions of dyestuffs according to the invention advantageously at temperatures of over 100 under pressure. Very good dyeings are also obtained if these fibers are impregnated with concentrated aqueous dispersion of dyestuffs according to the invention, the wrung out goods are dried and then the dying is fixed at temperatures of ISO-250. Dyeing can also be performed, however, at the boiling point of the dyebath in the presence of carriers such as phenylphenol, polychlorobenzene compounds or similar auxiliaries.

The drawing power of the dyestuffs can be further improved by mixing two or more anthraquinone dyestuffs according to the invention. Compared with dyeings made with previously known dyestuffs of similar constitution, the blue dye-ings attained on the fibers mentioned with the dyestuffs according to the invention have considerably improved fastness to sublimation and light and very good wet fastness properties.

The following examples illustrate the invention. Where not otherwise expressly stated, parts are given as parts by weight. The temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is as that of grams to cubic centimeters.

Example 1 33 parts of 1,5-dihydnoxy-4,S-dinitro-anthraquinone and 46.25 parts of 4-aminodiphenyl ether are heated for hours at 120125 in 500 parts of Z-ethoxyethanol, during which time the solution gradually turns a deep dark :blue color. On cooling the solution, the dyestutf formed of the formula precipitates in the form of fine violet blue tiny crystals; it is filtered off and dried. After recrystallisation from 2-ethoxyethanol, the product melts at 239-240"; it dissolves on warming in concentrated sulfuric acid with a yellow-green color and in pyridine or a mixture of xylenes with a blue color.

The finely distributed dyestuff dyes polyester fibers from an aqueous dispersion in very fast, clear, blue shades. If, instead of the 46.25 parts of 4-aminodiphenyl ether, the same number of parts of 3-aminodiphenyl ether are heated for 18 hours at the temperature given, then a somewhat reddish blue dyestutf is obtained which has similarly good fastness properties.

Example 2 Example 1 is repeated, but instead of 33 parts of 1,5-dihydroxy-4,8-dinitro-anthraquinone there are used 33 parts of 1,8-dihydroxy-4,S-dinitro-anthraquinone and instead of the 46.25 parts of 4-aminodipheny1 ether there are used 50.25 parts of 3-aminod-iphenyl thioether, all the other conditions remaining identical. The resulting dyestuff has similarly good fastness properties as those described in Ex ample 1.

OH(") OH to)! lH Example 3 First 33 parts of 1,8-dihydroxy-4,S-dinitro-anthraquinone and then 40.7 parts of S-aminodiphenyl ether are added at room temperature to 400 parts of distilled nitrobenzene. The mixture is heated for 30 minutes at while stirring well and simultaneously a stream of nitrogen is directed over the surface of the solution. At this temperature, the solution turns deep blue within 3 hours. The solution is cooled to 50, and 3000 parts of methanol are added. The dyestuff precipitates almost quantitatively out as a very fine dark powder of the formula r t RH This is filtered off and recrystallised from 2-ethoxyethanol. Violet crystals which melt at 206-207 are obtained. They dissolve in concentrated sulphuric acid with a brownish yellow, in pyridine and a mixture of xylene with a blue colour.

The dyestulf dyes fabric made from polyester fibers from an aqueous dispersion in clear, blue shades which have excellent fastness to light, wet and sublimation.

A very similar somewhat more greenish dyestuif is obtained on using 40.7 parts of 4-aminodiphenyl ether instead of the same number of parts of 3-aminodiphenyl ether.

Example 4 50.25 parts of 4-aminodiphenyl thioether are added to a paste of 33 parts of 1,5-dihydroxy-4,8-dinitro-anthraquinone in 350 parts of nitrobenzene and the mixture is heated at 180 to 185 until no more starting material can be traced. After removing the solvent by steam distillation, the condensation product of the formula NO: 0 OH is obtained from the deep 'blue solution obtained. It is filtered off, dried and recrystallised from pyridine. In this way, very fine blue small crystals are obtained which melt at 209-210. It dissolves in concentrated sulphuric acid with a dark green, in pyridine and in a technical xylene mixture with a blue colour.

The dyestufl dyes polyester material from a. finely distributed aqueous dispersion in greenish blue shades which have very good fasteners to wet, sublimation and light.

If instead of the 33 parts of 1,5-dihydroxy-4,8-dinitroanthraquinone, the same number of parts of 1,8-dihydroxy-4,5-dinitro-antraquinone is used, then a very similar but somewhat more greenish blue dyestutf having the sam excellent fastness properties is obtained.

Example 5 A mixture of 16.5 parts of 1,5-dihydroxy-4,8-dinitroanthraquinone and 16.5 parts of 1,8-dihydroxy-4,5-dinitroanthraquinone is heated to 180l85 with 50.8 parts of 4-amino-4'-methy1diphenyl ether in 350 parts of nitrobenzene. After 1% hours, the mixture of the dyestuffs formed of the formulae is precipitated by stirring the deep blue solution into 800 parts of ice-cooled methanol. The precipitate is filtered off, adhering nitrobenzene is removed by Washing with hot methanol and it is then dried.

The dyestuif dissolves in concentrated sulphuric acid with a greenish yellow, in pyridine and in a mixture of xylenes with a blue colour. The dyestuff dyes polyester fibres from a fine aqueous dispersion in deep blue shades and the dyeings have excellent fastness properties.

A considerably more greenish dyestuff is obtained if 54.83 parts of 4-amino-4'-methyldiphenyl thioether are used instead of 50.8 parts of 4-amino-4-methyldiphenyl ether, and a somewhat more reddish dyestufl? is obtained by replacing the 50.8 parts of 4-amino-4-methyldiphenyl ether by 47.18 parts of 3-arninodiphenyl ether.

Example 6 is obtained as a fine dark blue-violet powder. By repeated recrystallisation from 2-ethoxyethanol, the dyestufi is obtained in pure form as violet crystals which melt at 251- 252. It'dissolves in concentrated sulphuric acid with a blue, in pyridine and in a technical xylene mixture with a reddish blue colour. dyestuff dyes polyester fibres in intensive reddish blue shades. The dyeings have excellent fastness to light, sublimation and water.

From an aqueous dispersion, the

Very similar shades of the same excellent fastness are obtained by using 56.75 parts of 4-amino-3,5,4-trimethyldiphenyl ether, 60.25 parts of 4-amino-2,3,5,6-tetramethyldiphenyl ether, 57.25 parts of 4-amino-3,5-dimethyldi phenyl thioether, 53.25 parts of 3-amino-2,4-dimethyldiphenyl ether, or 58.25 parts of 4-amino-3,5-diethyldiphenyl ether instead of the 53.25 parts of 4-a=mino-3,5-dimethyldiphenyl ether. On the other hand, if in all cases the 33 parts of 1,5-dihydroxy-4,8-dinitro-anthraquinone are replaced by the same number of parts of 1,8-dihydroxy-4,5- dinitro-anthraquinone, then somewhat less strong reddish blue shades having the same gOOd fastness properties are obtained.

Example 7 66 parts of 1,5-dihydroxy-4,8-dinitro-anthraquinone and 96.5 parts of 4-amino-4-chlorodiphenyl ether in 400 parts of nitrobenzene are heated for 1 hour at 190 in a Weak stream of nitrogen, about 5 parts of Water being distilled off through a sloping condenser. A blue solution is formed. On cooling, the product of the formula crystallises out. A further amount of the product mentioned can be isolated by concentrating the mother lye. Its melting point, after recrystallisation once from nitrobenzene is 265267.

It is a shimmering crystal powder which dissolves in pyridine or in xylene with a blue and in concentrated sulphuric acid with a green colour.

From a fine aqueous distribution wit-h the addition of o-phenylphenol and a fatty alcohol polyethylene condensation product, the dyestuff dyes Dacron (of E. I. du Pont de Nemours) in reddish blue shades which have good fastness to light and excellent fastness to sublimation.

If in the above example, the 96.5 parts of 4-amino-4'- chlorodiphenyl ether are replaced by the same amount of 4-amino-2'-chlorodiphenyl ether or by 117 parts of 4 amino-3'-methyl-4'-chlorodiphenyl ether, then dyestufis having the same properties are obtained.

Example 8 46.8 parts of the dyestuff produced according to Example 1 of the formula are dissolved hot in 200 parts of .abs. nitrobenzene. The solution is cooled to 20-25 and then a solution of 16 parts of bromine in 40 parts of abs, nitrobenzene is added dropwise within 1 hour. The whole is stirred for another 15 hours at 20-25" whereupon the dyestuff m-onobrominated in the diphenyl ether group gradually precipitates. The precipitation is completed by diluting the mixture with methanol. The new dyest-ufi dyes polyester fibres from an aqueous dispersion in somewhat more reddish blue shades than the unbrominated dyestuff. The dyeings have excellent fastness to sublimation.

A dyestufi monohalogenated in the diphenyl ether group having the same properties is obtained starting from the condensation product of 1,S-dihydroxy-4,8-dinitro-anthraquinone and 4-a-mino-3'-methyldiphenyl ether, by afterbrominating this condensation product or also after-chlorinating in an analogou manner by introducing chlorine into the nitrobenzene solution.

Example 9 bution and 100 parts of terepht'halic acid polyglycol ester 10 fabric are dyed for 1 /2 hours at 9598. The dyeing is rinsed and thoroughly washed with dilute sodium hydroxide solution and a dispersing agent such as, eg the condensation product of naphthalene sulphonic acid and formaldehyde. A blue dyeing which is fast to light, wet 15 and sublimation is obtained.

Example 10 2 parts of the finely ground dyestulf mixture obtained according to Example 4 are distributed in 4000 parts of water which contain 2 parts of a condensation product of naphthalene sulphonic acids and formaldehyde. The pH of the dyebath is adjusted to 6.5 with acetic acid. 100 parts of terephthalic acid polyglycol ester fabric are introduced at 40, the bath is heated within 15 minutes to 120 in an autoclave and kept for 45 minutes at this temperature. The dyeing is rinsed with water and then soaped. A clear blue dyeing is obtained which has excellent fastness to light, wet and sublimation.

The following table gives the shades of dyeings on Dacron obtained with other dyestuifs which can be produced by methods analogous to those described in the foregoing examples.

TABLE I.Coutinued No Y1 Y1 NHA Shade on Dacron nn 31-13 28..-, N: OH NH-0- Reddish I blue. C2H5 29 NO: OH NH S Blue.

3o OH NO: -NH- 0Q Do.

:H5 31.... N01 OH -NH@ (3H3 Do.

a2- NO: OH NH-S Do.

What we claim is: 1. A dyestuif of the formula a l? I'm wherein:

N02 0 OH 3. A dyestuif of the formula OH (I? OH 4. A dyestulf of the formula NO: (H) (FH 5. A dyestuff of the formula R ll r 6. A dyestuff of the formula N0 (6 OH 7. A dyestufi' of the formula NO: (I? OH References Cited by the Examiner UNITED STATES PATENTS 2,845,443 7/1958 Hindermann et a1. 26038O X LORRAINE A. WEINBERGER, Primary Examiner.

H. C. WEGNER, Assistant Examiner. 

1. A DYESTUFF OF THE FORMULA 